Journal of Oral Rehabilitation
Journal of Oral Rehabilitation 2011 38; 295–314
Review Article
Self-adhesive resin cements – chemistry, properties
and clinical considerations
J. L. FERRACANE*, J. W. STANSBURY† & F. J. T. BURKE‡
Division of Biomaterials and Biomechanics, Oregon Health & Science University, Portland, OR, Department of Craniofacial Biology, School of
Dental Medicine, University of Colorado Denver, Aurora, CO, USA and ‡Primary Dental Care, University of Birmingham School of Dentistry,
Birmingham, UK
SUMMARY Self-adhesive resin cements were intro-
duced to dentistry within the past decade but have
gained rapidly in popularity with more than a dozen
commercial brands now available. This review arti-
cle explores their chemical composition and its
effect on the setting reaction and adhesion to
various substrates, their physical and biological
properties that may help to predict their ultimate
performance and their clinical performance to date
Introduction
Self-adhesive resin cements, defined as cements based
on filled polymers designed to adhere to tooth structure
without the requirement of a separate adhesive or
etchant, were introduced to dentistry within the past
decade but have gained rapidly in popularity, with
more than a dozen commercial brands now available.
The major benefit of these materials would appear to be
simplicity of application. While a reasonable body of
literature has been generated describing the properties
and adhesion of these materials to various substrates,
the vast majority of the literature has described one
cement, RelyX Unicem*, which was the first commer-
cial product. Relatively little information exists about
the composition and mechanism of adhesion of these
materials, and scant independent evaluation of their
clinical efficacy has been reported.
Most dental practitioners are very familiar with the
qualities and uses of the cements that historically have
been used most frequently, such as zinc phosphate,
*3M ESPE, St. Paul, MN, USA.
ª 2010 Blackwell Publishing Ltd
*Department of Restorative Dentistry,
†
and handling characteristics. The result of this
review of self-adhesive resin cements would suggest
that these materials may be expected to show
similar clinical performance as other resin-based
and non-resin based dental cements.
KEYWORDS: dental cement, self-adhesive, self-etch,
properties, clinical performance
Accepted for publication 10 July 2010
glass–ionomer and resin composite. However, dentists
may still experience confusion over the specific com-
position and indications for other types of ‘hybrid’
cements, such as resin-modified glass–ionomer and
polyacid-modified resin (compomers). Because of their
relative newness and the comparative lack of availabil-
ity of scientific evidence, most dentists are likely to be
even more confused about the indications and expec-
tations for the so-called self-etch or self-adhesive
cements. A recent review article provided an extensive
presentation of much of the previous literature on self-
adhesive resin cements (1). This work serves as a useful
base upon which to further investigate these interesting
materials from several different perspectives. Specifi-
cally, this article will explore what is known or can be
inferred about their chemical composition and its effect
on the setting reaction and adhesion to various
substrates, their physical and biological properties and
other materials science aspects that may help to predict
their ultimate performance, and the important clinical
considerations that will determine their indications,
handling and limitations when used by the dental
practitioner.
doi: 10.1111/j.1365-2842.2010.02148.x
296 J . L . F E R R A C A N E et al.
Dental cements – evolution of the
materials
Self-adhesive cements are hybrid materials that com-
bine features of composite restoratives, self-etching
adhesives and, in some cases, dental cements. The
rational design of dental composites, including the
development of dimethacrylate monomers specifically
for application in resin-based composites, was advanced
by Bowen (2–5). When coupled with Buonocore’s acid
etching technique (6) to promote adhesion to enamel,
resin composite restorative materials began to emerge
as viable clinical options. The incorporation of acid-
functionalised methacrylate or related monomers is a
critical component in self-adhesive resin cements
because effective chemical bonding to tooth requires a
polyacid matrix structure, whether based on a pre-
formed polyalkenoate or one that is created in situ
during a curing process involving acidic monomers.
Progress in dental cements based on polyacids can be
traced from polyalkenoate cements, which consist of
zinc polycarboxylate cements (7) and glass–ionomer
cements (GIC) (8), both of which set as the result of an
acid–base reaction within an aqueous environment.
These were followed by resin-modified glass–ionomer
cements (RMGICs) (9–12) that rely on the formation of
a methacrylate-based network to augment the ionic
cement structure through either grafting polymerizable
double bonds onto a polyalkenoate backbone or by the
incorporation of free radically polymerizable methac-
rylate monomers in the cement composition. Relatively
hydrophilic monomers are used in RMGICs because
these remain water based with the acid–base reaction as
the primary setting mechanism. Like the polyalkeno-
ates, RMGICs maintain the ability to bond to hard tooth
tissues through the presence of linked acidic functional
groups capable of chelation with the calcium in
hydroxyapatite (13–15). Soon after RMGICs, compo-
mers were introduced with the intent to combine the
benefits of composites and glass–ionomers (16). Comp-
omers typically consist of mono-, di- or multi-methac-
rylate monomers, polycarboxylates, as well as some
(meth)acrylate monomers bearing pendant carboxylic,
phosphoric or related acidic functional groups. The filler
is similar to the ion-leachable glass present in GICs but
may be partially silanised to achieve some covalent
attachment with the matrix. There is little or no water
included in the compositions, and the primary mode of
curing is the free radical polymerisation reaction.
Compomers are not inherently able to bond directly
to hard tooth tissues (17, 18), and they release
significantly lower levels of fluoride than GICs (19, 20).
The previous discussion provides the materials con-
text for the introduction of self-adhesive resin cements,
of which RelyX Unicem from 3M ESPE* represents the
first of this new class of materials. These materials are
most similar in nature to compomers with the primary
difference being the acidic monomer concentration.
Also, in most cases, self-adhesive resin cements have a
somewhat lower filler content compared with compo-
mers, and because of the limited luting cement thick-
ness in bonding applications, hydrated substrates more
efficiently facilitate ionisation of the acidic monomers
followed by acid–base neutralisation reactions involv-
ing the tooth and the basic filler. These are important
distinctions because, unlike compomers, the self-
adhesive resin cements do offer a reasonable degree of
unassisted adhesion to dentin although bonding
directly with enamel still presents a greater challenge.
Beyond the bonding to tooth structure that is possible
with these polymer-based acidic matrices, the ability of
self-adhesive resin cements to deliver fluoride ions
owing to partial acid dissolution of suitable soluble glass
filler also may be considered significant; though, clin-
ical evidence has yet to be demonstrated. Self-adhesive
cements that lack the glass–ionomer fluoride leachable
filler may, by inclusion of sodium fluoride or related
salts as a component of the cement, still provide a
source for fluoride release.
Chemical composition – self-adhesive resin cements
There are more than one dozen self-adhesive resin
cements on the market at the time of this writing
(Table 1). Specific compositions for commercial mate-
rials can be found in the manufacturer’s literature, and
have been published in several articles (1, 17, 18) and
are summarised in Table 1. In some cases, details about
the composition of the two components for each
cement have been provided by the manufacturers,
and other cases not.
The current self-adhesive resin cements are two-part
materials that require either hand mixing, capsule
trituration or delivery by an auto-mixing dispenser.
One component is comprised of conventional mono-,
di- and ⁄ or multi-methacrylate monomers that are used
in a variety of resin-based dental materials: Bis-GMA,
urethane oligomers of BisGMA, UDMA, HEMA, glycerol
ª 2010 Blackwell Publishing Ltd
 SELF-ADHESIVE CEMENTS 297

Table 1. Brands and compositions of self-adhesive resin cements circa 2009

Cement Manufactures Composition

BisCem Bisco* Bis(hydroxyethyl methacrylate) phosphate, tetraethyleneglycoldimethacrylate, glass filler

Breeze Pentron† Not available
Bifix SE Voco‡ Bis-GMA, UDMA, Gly-DMA, phosphate monomers, initiators, stabilisers, glass fillers, aerosol silica
(filler = 70 wt%; 61 vol%; avg. 2 lm)
Clearfil SA Kuraray§ MDP, hydrophobic aromatic dimethacrylate, hydrophobic aliphatic dimethacrylate, colloidal silica,
Cement barium glass (filler = 66 wt%; 45 vol%; avg. 2Æ5 lm)
Embrace Pulpdent¶ Not available
Wet Bond
G-Cem GC** Powder = fluroaluminosilicate glass, initiator, pigment (filler = 71Æ4 wt%, avg. 4 lm)
Liquid = 4-MET, phosphoric acid ester monomer, water, UDMA, dimethacrylate, silica powder,
initiator, stabiliser
iCem Heraeus†† Di-, tri- and multi-functional acrylate monomers, initiators, stabilisers (filler = 41 vol%)
Maxcem Elite Kerr‡‡ Powder = barium aluminosilicate glass, fluoroaluminosilicate glass, nano-ytterbium fluoride,
nanosilica (filler = 67 wt%, avg. 3Æ6 um – orig. Maxcem)
Liquid = GPDM monomer, mono-, di- and multi-methacrylate co-monomers; redox initiator system,
camphorquinone-based photoinitiator
Monocem Shofu§§ Mono-, di- and multi-functional acrylate resins, dual-initiators, fillers (filler = 60 wt%)
Multilink Sprint Ivoclar¶¶ Dimethacrylate monomers, acid monomers, barium glass fillers, ytterbium trifluoride, silicon dioxide
(filler = 57 wt%; avg. 5 lm)
RelyX Unicem 3M ESPE*** Powder = glass, silica, calcium hydroxide, pigment, substituted pyrimidine, peroxy compound,
initiator (filler = 72 wt%; avg. <9Æ5 um)
Liquid = methacrylated phosphoric ester, dimethacrylate (bis-GMA ⁄ TEGDMA), acetate,
stabiliser, initiator
seT SDI††† Not available
Smart Cem 2 Dentsply‡‡‡ UDMA, Di- and Tri-methacrylate resins, phosphoric acid modified acrylate resin, fluroaluminosilicate
glass initiators, accelerators, stabilisers, butylated hydroxyl toluene, titanium dioxide, hydrophobic
silica (filler = 69 wt%; 46 vol%; avg. 3Æ8 lm glass and 16 nm aerosol silica)
Speed Cem Ivoclar¶¶ Dimethacrylates, methacrylated phosphoric esters, copolymers, initiators, catalysts, stabilisers barium
glass, ytterbium trifluoride, high dispersed silica (filler = 40 vol%; size 0Æ1–7 lm)

*Bisco Inc., Schaumburg, IL, USA.

†
Pentron, Wallingford, CT, USA.
‡
Voco, Cuxhaven, Germany.
§
Kuraray America, New York, NY, USA.
¶
Pulpdent, Watertown, MA, USA.
**GC, Alsip, IL, USA.
††
Heraeus, Hanau, Germany.
‡‡
Kerr, Orange, CA, USA.
§§
Shofu, Kyoto, Japan.
¶¶
Ivoclar Vivadent, Schaan, Liechtenstein, Germany.
***3M ESPE, St. Paul, MN, USA.
†††
SDI, Victoria, Australia.
‡‡‡
Dentsply, Konstanz, Germany.

dimethacrylate (GDMA), TEGDMA, trimethyloylpro-
pane trimethacrylate (TMPTMA) and many others
(Fig. 1).
The acid-functionalised monomers currently utilised
to achieve demineralisation and bonding to the tooth
surface are still predominantly (meth)acrylate mono-
mers with either carboxylic acid groups (Fig. 2), as with
4-methacryloxyethyl trimellitic anhydride (4-META)
and pyromellitic glycerol dimethacrylate (PMGDM), or
phosphoric acid groups (Fig. 3), as with 2-methacryl-
oxyethyl phenyl hydrogen phosphate (Phenyl-P),
10-methacryloxydecyl dihydrogen phosphate (MDP),
bis(2-methacryloxyethyl) acid phosphate (BMP) and
dipentaerythritol pentaacrylate monophosphate (Pen-
ta-P). There are substantial numbers of new proprietary
acidic monomers, primarily those based on phosphates
and phosphonates that have been developed specifi-
cally to perform the surface demineralisation of enamel

ª 2010 Blackwell Publishing Ltd

298 J . L . F E R R A C A N E et al.

O O

O O O O

OH OH
BisGMA
O O
H
O N O
O N O
H
O UDMA O

OH O
O
O O
OH O
O
O HEMA GDMA O
O O
O O

O O O
O O

TEGDMA TMPTMA
O

Fig. 1. Non-acidic methacrylate monomers used in resin adhesive cements.

O O
O O
N N
N N Fig. 2. Examples of hydrolytically
stable, cross-linkable bisacrylamides
for potential use as comonomers in
DEAAP DBAAP
strongly acidic formulations.

and dentin as well as to promote stable salt formation,
mainly involving calcium. The selection of the acidic
monomer structure is critically important as exempli-
fied by the formation of a strong, aqueous insoluble salt
complex between calcium and the relatively hydro-
phobic MDP, whereas 4-Met and Phenyl-P produce a
calcium complex with more limited stability to disso-
lution (15, 21, 22).
The concentration of the acidic monomers in these
materials must be balanced to be low enough to avoid
excessive hydrophilicity in the final polymer but high
enough to achieve an acceptable degree of self-etching
character and bonding to dentin and enamel. Free
radical polymerisation of the acidic monomers to some
degree replicates the adhesive potential of polyalkeno-
ate cements, and it allows the ratio of acidic to non-
acidic comonomers to be fully controlled. Excessive
hydrophilic character can cause swelling that may
compromise mechanical strength as well as dimen-
sional stability. As initially mixed, the cements are fairly
hydrophilic, which facilitates their wetting of and
adaptation to the tooth surface. But the materials
become more hydrophobic as the acid functionality is
consumed through reaction with calcium on the tooth
and a variety of metal oxides from the ion-leachable
filler. The fillers used are composed of combinations
selected from barium fluoroaluminoborosilicate glass,
strontium calcium aluminosilicate glass, quartz, colloi-
dal silica, ytterbium fluoride and other glass fillers. The
partial surface dissolution of acid-soluble glass serves to
neutralise the resin acidity and is capable of delivering
sodium, calcium, silicate and fluoride ions that can
either take part in the setting reaction or be released
locally. The total filler content is typically in the range
of 60–75 wt% (23). The necessity for segregation of the
materials arises to avoid premature acid–base interac-
tions between the acidic monomer and the ion-leach-
able glass as well as to allow separation of the redox
initiator components that promote the free radical
chemical curing process. In addition, to provide access
to a free radical photoinitiated mechanism to be used in
conjunction with the redox curing, a tertiary amine or

ª 2010 Blackwell Publishing Ltd

 SELF-ADHESIVE CEMENTS 299

O OH
O O
O OH O
CH2 O
10 O
O O O
MAC-10 4-META
O
O O

O
O OH

O OH

4-MET
O

Fig. 3. Carboxylic acid monomers used to promote adhesion in cements.

some other electron-donating compound used as the
photo-reductant must be isolated from the acidic
monomers to prevent deactivation of the photoinitiator
as well as a gradual spontaneous polymerisation process
that limits the shelf life of monomers in the presence of
acidic and amine functionalities.
Current developments of acidic monomers and acid-stable
resin formulations
Self-adhesive resin cements critically rely on strongly
acidic monomers that impose formulation stability
complications. Because material manufacturers often
do not fully disclose compositional details, a review of
current progress involving acidic monomers is included
here although it must be noted that most are these new
monomers are likely in development for dental adhesive
applications. There are a variety of recently developed
neutral monomers based on bisacrylamide structures,
such as bisacrylamido-N,N¢-diethyl-1,3-propane (DEA-
AP; Fig. 4), as well as a dibenzyl analog (DBAAP)
mentioned in the patent literature, that combine good
biocompatibility with enhanced hydrolytic stability
under aqueous acidic conditions when compared with

OH OH OH
Phosphate s O P OH O P O Phosphona tes P OH

O O O

OH
O O
CH2 P OH
10
O O
MDP
O O
O
OH
O P O
O O HO P
OH MAEPA
O Phenyl-P O

O
H O
O P O N
O O P OH
OH
O O O OH
BMP MAMPA

Fig. 4. Generalised structures of phosphate and phosphonate functional groups and examples of their use in self-etching dental
monomers.

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300 J . L . F E R R A C A N E et al.
H O
N N
S O
O OH O O
AMPS
Fig. 5. An extremely acidic sulfonic acid acrylamide monomer (AMPS) as well as examples of new acrylamide monomers with the
potential to vary the spacer length bridging to the phosphonate group (NMADP) or the length of the N-alkyl substituent as well as the
number of phosphonate groups (NPAPBP).
methacrylates (24, 25). Acrylamide reactive groups are
preferred because N,N-disubstituted methacrylamides
are less efficient in homopolymerisations or in copoly-
merisations with methacrylate monomers. There is no
clear indication from product labels that these and other
bisacrylamide monomers are being used currently in
any of the adhesive resin cements, but their develop-
ment as acid-resistant components for strongly acidic
formulations appears well suited for this application.
It appears that relatively limited use has been made
of acidic monomers based on sulfonic acid, such as
2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS)
(Fig. 5). While the sulfonic acids are extremely strong
acids with pH levels approaching 0, this actually limits
their practical utility because of potential hydrolytic
instability of the attachment between the acidic func-
tionality and the polymerizable group. This explains the
use of the more hydrolytically stable acrylamide group in
the AMPS structure rather than reliance on a methac-
rylate ester. Further examples of novel monomers
designed specifically for use in hydrolytically stable,
self-etching dental adhesives are 10-(N-methylacrylam-
ido)decylphosphonic acid (NMADP) and 3-(N-propyl-
acrylamido)propylidenebisphosphonic acid (NPAPBP)
(26, 27).
Besides the use of (meth)acrylamides to enhance
the hydrolytic stabilities of acidic monomers and the
comonomers with which they are formulated, an
O OH
O
O P OH
OH
AOEP
O O
P OH N P OH
CH2 OH
10 OH
O P
OH
NMADP NPAPBP OH
alternate approach is demonstrated with 2,4,6-tri-
methylphenyl-2-[4-(dihydroxyphosphoryl)-2-oxabutyl]-
acrylate (MAEPA; Fig. 3) (28). This monomer has the
benefit of a hydrolytically stable ether linkage rather
than an ester as the connection between the poly-
merizable vinyl group and the phosphonate function-
ality. It also contains a bulky hydrophobic substituent
as its ester substituent and thereby can be expected to
provide reasonable overall stability in acidic media. In
comparison with methacrylate monomers, some
restriction in reactivity may be encountered for the
more sterically encumbered vinyl group of this type,
but overall, their polymerisation behaviour is fairly
similar to and compatible with methacrylate mono-
mers (29).
Another method to obtain acid-stable monomers that
appears to be in development for application in self-
etching dental resins involves the use of monomers
bearing allyl ether reactive groups (30). This strategy
may be practical in a two-part formulation where
the hydrolytically stable allyl ether linkage, such as
in allyloxyethylphosphate (AOEP: Fig. 6) or 2-(al-
lyloxymethyl)-2-ethylpropane-1,3-diyl bis(dihydrogen
phosphate) (AOMEPB), can tolerate an acidic storage
environment but rely on copolymerisation with more
reactive comonomers from the second neutral mono-
mer component to overcome the inherent low free
radical reactivity of allyl ethers.
O P OH
O
O
O P OH Fig. 6. Examples of acidic mono-
AOMEPB
mers with allyl ether polymerizable
OH groups.
ª 2010 Blackwell Publishing Ltd

Curing chemistry
A self-curing or redox chemical curing mode of poly-
merisation is an essential feature of resin-based dental
cements because the restricted access to adequate light
intensity in most indirect restorations precludes the use
of photo-initiated polymerisation alone. While some
materials are designed to employ a self-curing mode
exclusively, most self-adhesive cements promote the
use of a dual chemical and photochemical cure based
on the addition of photo-initiators along with the redox
initiators. The combined access to a chemical cure,
which commences only gradually upon mixing the
two-part material components and only after the
inhibitor has been consumed, with photo-initiation,
which provides a rapid, on-demand boost to the setting
process, allows improved final conversion and adhesive
strength properties compared with the self-cure alone.
Several studies have indicated substantial improve-
ments in the methacrylate conversion levels when the
dual light and chemical curing modes are compared
with self-curing alone (31, 32).
The acid–base reaction between the acidic function-
ality on the monomers and the acid-soluble glass or the
mineralised tooth surface is initiated upon mixing of
the two components and placement of the cement on
the tooth. The acid–base reaction rate is also control-
lable through physical factors such as water content,
ion solubility and diffusion constraints. There is some
mention in patent literature of encapsulation strategies
to either isolate certain reactive components or simply
to retard the onset of the acid–base reaction process.
Similarly, the free radical redox polymerisation pro-
cess involving the methacrylate monomers could start
potentially at the time of mixing; however, in practice,
the added inhibitor used to extend the shelf life of the
material also provides a controllable inhibition or
working time that allows a sufficient interval for mixing
and placement of the cement. A working time of
S
NH
OOH
H2N
CHP BTU
Fig. 7. Cumene hydroperoxide (CHP) is an example of an acid-resistant oxidising agent that can be used with a urea or thiourea, such as
benzoyl thiourea (BTU). Sodium benzene sulfinate (SBS) provides means to recover reactivity in acid sensitive initiating systems. Redox
curing based on barbituric acid derivatives, such as DPBA, has received limited attention as acid-resistant initiators.
ª 2010 Blackwell Publishing Ltd
SELF-ADHESIVE CEMENTS 301
approximately two minutes is typical with setting times
for self-polymerising systems ranging from about three
to seven minutes, with some manufacturers specifying
room temperature and others indicating oral tempera-
ture (1). Once the material has been placed, the
restoration seated and excess cement removed from
around the restoration, the photocuring process can
then be augmented with a 20- to 40-s exposure to
visible light from a conventional dental curing unit to
significantly increase the rate of the free radical poly-
merisation process that creates the cross-linked meth-
acrylate network.
Unlike the redox systems utilised in self-curing
denture base materials, which employ benzoyl peroxide
and tertiary amines as the oxidant and reductant,
respectively, the low pH conditions present in the acidic
component of the self-adhesive resin cements compli-
cate or preclude the use of both of these initiating
species. In redox polymerisations, benzoyl peroxide is
susceptible to radical formation in acidic environments
and amines form salts that greatly decrease their
activity with peroxides even more so than in the case
of amines used as photoreductants with a photosensi-
tiser (33). Instead, an acid-tolerant oxidant, such as
cumene hydroperoxide (CHP; Fig. 7), is used in the
acidic part of the formulation, while various thioureas,
such as benzoyl thiourea (BTU), are employed as the
reducing agent in the non-acidic part (24). To induce
visible light activity so that conventional dental curing
lights can be used to advance a photocuring comple-
ment to the polymerisation reaction, camphorquinone
(CQ) and ⁄ or diphenyl-(2,4,6-trimethylbenzoyl) phos-
phine oxide (TPO) is added to the acidic components,
while a tertiary amine, such as ethyl N,N-dim-
ethylaminobenzoate (EDMAB) or N,N-dimethylamino-
benzonitrile, is incorporated with the non-acidic
components. Redox initiators and, to a lesser extent,
photoinitiators were found to be sensitive to acidic
monomers, and the acid resistance of both types of
O
O
N
S
O- Na+ O N O
SBS DPBA
302 J . L . F E R R A C A N E et al.
initiators was improved by the addition of sodium aryl
sulphates (SBS) and aryl borate salts (33). The
reference to a substituted pyrimidine in the RelyX
Unicem cement product literature may be related to
barbituric acid derivatives, such as 1,3-dimethyl-
5-phenyl barbituric acid (DPBA), that have been used
in acidic redox initiating systems in place of conven-
tional amines.
The acidic monomers, depending on the type and
concentration of acid functionality as well as the
moisture content, create a pH between ca. 1Æ5 and 3
in the freshly mixed cement, which is certainly acidic
enough to demineralise hard tooth surfaces. As the
acid–base reaction proceeds, ionic cross-links that form
between acid groups and calcium or aluminium ions
cause the pH to rise. Some materials include calcium
hydroxide, which is isolated in the non-acidic part of
the formulation, likely to contribute to a more rapid
neutralisation process rather than simply being present
for its antimicrobial action. Also associated with the
neutralisation process, the cement converts from a
relatively hydrophilic paste that readily wets moist
dentin and enamel to a fairly hydrophobic state that
limits post-cure swelling and material deterioration.
The reaction kinetics of the setting process of self-
adhesive resin cements has received little attention to
this point. There is manufacturer literature from 3M
ESPE* showing the neutralisation kinetics for RelyX
Unicem in self-curing mode taking longer than that
associated with the dual-cure activation. There is a
rapid initial rise in pH from approximately 2–4 over the
first hour of the setting process followed by a long
gradual continued rise in pH that approaches 7 by
24–48 h. One independent study also reported a neu-
tral pH for this cement at 48-h post-cure (34). Clearly,
the curing temperature (room or oral) will significantly
affect the rate of the setting process. One study has
looked into the use of pre-heated delivery to the
cement as a means to potentially improve adaptation
with the tooth as well as to raise conversion levels and
found that working time was less than that needed for
the mixing process at 60 C but not at 37 C (35).
Dynamic dimensional change and shrinkage stress up
to 1 h were monitored for Maxcem, Multilink Sprint
and RelyX Unicem in their self-curing and dual curing
modes (36). With self-curing, both Maxcem and Mul-
tilink Sprint produced dramatically higher shrinkage
strain rates and greater shrinkage than RelyX Unicem.
With similar 1-h methacrylate conversion levels
reported for Maxcem and RelyX Unicem, it appears
likely that the reduced shrinkage noted for the latter
arises because of expansion effects related to the acid–
base reaction involving the soluble filler and other basic
components such as calcium hydroxide that partially
counter the shrinkage derived from the methacrylate
polymerisation. However, in the much faster dual-cure
mode that preferentially affects the methacrylate curing
reaction as opposed to the acid–base reactions, only the
RelyX Unicem material shows a higher shrinkage value
than that obtained in the self-cure mode.
Proposed mechanism of adhesion
The setting reaction of RelyX Unicem as detailed in the
commercial literature emphasises the free radical meth-
acrylate polymerisation process as the primary reaction
mode. This is activated by chemical and photochemical
routes to begin the cross-linking polymerisation of
monomers with and without phosphoric acid function-
ality. The acidic groups bind with calcium in the
hydroxylapatite to form a stabilising attachment
between the methacrylate network and the tooth. Ions
released from the acid-soluble filler neutralise the
remaining acidic groups to create a chelate reinforced
three-dimensional methacrylate network. There have
been at least three studies that have focused on the
reaction between the acidic monomer components of
these cements and calcium in the form of powdered
hydroxylapatite or upon placement on dentin and
enamel surfaces (37–39). There appears to be agree-
ment that there is very limited interaction with enamel
or dentin in terms of either smear layer demineralisa-
tion or tag formation. However, there are indications by
X-ray photoelectron spectroscopy (XPS) of good chem-
ical interaction with calcium from hydroxylapatite,
which suggests that this latter route provides a means
to micromechanical retention even though there is no
significant infiltration of more than a micrometre into
the dentinal surface (40).
Physical properties of self-adhesive resin
cements
Physical ⁄ mechanical ⁄ wear properties
There are few studies that have examined the mechan-
ical properties of self-adhesive resin cements, compar-
ing them to other types of cements. Perhaps the most
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 SELF-ADHESIVE CEMENTS 303

Flexure Strength vs Cement Type non-self-adhesive resin cement in either self- or dual-
100 P-2003 cure mode.
90 The Behr et al. (42) study also showed the abrasion
K-2004
80
B-2008 wear of the self-adhesive resin cement when self-cured
70
to be substantially greater than that of non-self-adhe-
60
sive resin cement and glass–ionomer, and equivalent to
50
zinc phosphate, though less than resin-modified glass–
40
30
ionomer, which had the highest wear. In contrast, a
20
study of toothbrush abrasion of a zinc phosphate
10 cement placed between ceramic blocks, representing
0 cement in a luting space, showed much higher wear
ZOP GIC RMGIC RC-sc RC-dc SA-sc SA-dc PC
than Unicem when simulating 5 years of wear (about
22 versus 5 micrometre) (43). Whereas these data are
Fig. 8. Flexure Strength versus Type of Cement (data compiled somewhat contradictory, they may be explained by the
from P = Piwowarczyk and Lauer, 2003; K = Kumbuloglu et al.
differences in the test methods, in that the toothbrush-
2004; and B = Behr et al. 2008).
ing test, while clinically relevant, likely presents a much
less aggressive mechanical force than the three body
comprehensive is the study of Piwowarczyk and Lauer
wear test used by Behr et al. (42). Perhaps the most
(41), which compared the flexure and compressive
clinically relevant test of wear has been conducted by
strength of a self-adhesive resin cement, Unicem (3M
placing these cements into a gap between two ceramic
ESPE*), to two zinc phosphates, two glass–ionomers,
surfaces, as would occur clinically (23). Wear tests were
three resin-modified glass–ionomers and four dual-cure
performed by toothbrush abrasion, as well as with the
resin cements. The self-adhesive resin cement tested
ACTA wear machine using an abrasive slurry of millet
either in the self-cure (SA-sc) or dual-cure (SA-dc)
seeds pressed between the material and a rotating steel
mode had nearly equivalent to slightly lower flexure
disk. The authors showed that the eight self-adhesive
and compressive strength than other resin cements
resin cements tested generally had good resistance to
(RC-sc and RC-dc), but both types were much stronger
toothbrush wear but showed more accelerated wear
than zinc phosphate (ZOP), GIC, or RMGIC (Fig. 8).
than non-adhesive resin cements or a flowable com-
The dual-cure cements were slightly stronger than self-
posite when tested in the ACTA machine with higher
cure versions at 1 day, but when retested after storage
abrasion forces. This would suggest that the self-
in water for 150 days, there was no difference between
adhesive resin cements would likely perform well
the two. This was attributed to the fact that the dual-
clinically when exposed to abrasion predominantly
cured Unicem showed a significant reduction in both
created by the toothbrush or food excursions under a
flexure and compressive strength with ageing.
minimal load, but on occlusal surfaces, where forces are
In another study, the flexure strength of the same
higher, material loss at the margins from abrasion
self-adhesive resin cement, Unicem, was lower than
during chewing or grinding may be greater than that
that of a resin cement, while the compressive strength
seen in other resin cements.
showed the opposite relationship (31) (Fig. 8). Both
In a recent study, four self-adhesive resin cements
cements were stronger than polycarboxylate (PC). In a
(G-Cem§; Maxcem, Kerr‡; Smart Cem¶; and Unicem,
more recent study, Behr et al. (42) showed similar
3M ESPE*) were shown to be very susceptible to
flexure strengths for a resin cement, Panavia F† (Fig. 8),
surface erosion when exposed to acetic acid and
and a self-adhesive resin cement, Maxcem‡, but
acetone, with the least affected cement being Unicem
showed the strength of the self-adhesive resin cement
(34). Some surface erosion and loss of particles occurred
to be drastically reduced when mixed with 10% less of
in water as well. Other studies have shown less surface
the catalyst paste, independent of whether it was self-
degradation of dental composites versus glass–ionomers
or dual-cured. This study also showed the hardness of
in acidic solutions (44, 45). The fact that the erosion
the self-adhesive resin cement to be lower than that of a

† §
Kuraray America, New York, NY, USA. GC, Alsip, IL, USA.
‡ ¶
Kerr, Orange, CA, USA. Dentsply, Konstanz, Germany.

ª 2010 Blackwell Publishing Ltd

304 J . L . F E R R A C A N E et al.
seems to be more extensive on the self-adhesive resin
cements than has generally been shown for dental
composite restoratives is likely due to the more hydro-
philic nature of the matrix resin in the self-adhesive
resin cements. In addition, to allow them to react with
the acidic monomers in the matrix, the surface of the
basic fillers in these cements is less protected than those
in restorative composites owing to the absence of a
hydrophobic resin coating, such as silane.
The overall examination of the strength, hardness
and wear of the two brands of resin cements reported in
the studies mentioned earlier suggest that their resis-
tance to fracture and wear may be similar to, or perhaps
slightly lower than, that of non-self-adhesive resin
cements. However, the self-adhesive resin cements
are in general superior to the non-resin based
cements, such as zinc phosphate, polycarboxylate and
the glass–ionomers in this regard. As current clinical
studies are only short term, it is not yet possible to
determine whether these subtle differences will have a
significant clinical effect.
Adhesion to different substrates
Resin cements must bond to a variety of different
substrates, including dentin and enamel, porcelain and
other ceramics, gold and other metal alloys, and indirect
resin composites. The self-adhesive resin cements were
designed specifically to interact with the dentin sub-
strate with minimal additional surface preparation.
While historically bonding to enamel through the use
of phosphoric acid etching has been effective, these new
cements use alternative acids that may not produce
equivalent mechanical etch patterns for adhesion. Thus,
a result that was taken for granted can no longer be
until verified through appropriate testing. The same can
be said of the adhesion to the restorative and prosthetic
materials used for indirect restorations.
Teeth. A number of studies have been conducted on
adhesion to dentin and enamel, predominantly on
RelyX Unicem, but also for other self-adhesive resin
cements. These studies typically have compared the
bond to tooth structure with the cement sandwiched
between another substrate representing an indirect
restorative material, such as ceramic, metal or labora-
tory processed dental composite. However, in the
studies, the interface of interest has been that between
the cement and the dentin or enamel.
Numerous studies have evaluated the bond strength
of self-adhesive resin cements to human dentin and
enamel substrates using microtensile (38, 46–51), shear
(52–56) or tensile (39) testing modes. The bond to root
canal dentin has also been reported using a micro push
out test (57). The majority of these studies evaluated
RelyX Unicem as the self-adhesive resin cement, and
typically in comparison with Panavia F in addition to
other cements employing self-etch or etch-and-rinse
adhesives. However, Maxcem, Maxcem Elite, Multilink
Sprint and iCem were other self-adhesive resin cements
tested at least once. In addition, bovine dentin was used
in one study to compare the micro-tensile bond
strengths of Unicem, Panavia F and Fuji Cem GIC (46).
Although it is somewhat difficult to draw strong
conclusions from the data because of the limited
number of studies testing under comparable conditions,
i.e. same cements, same substrates, same curing and
storage conditions, etc., the data do suggest that the
bonding of Panavia F and Variolink II to human dentin
and enamel, when used with their associated primers
and ⁄ or etchants, is superior to that of Unicem (Fig. 9).
Analysis of the bond joint after testing shows that, in
general, the failure of Unicem to enamel is mostly
adhesive, while the failure to dentin is adhesive or a
mixed-mode. Also, when other resin cements were
included in the comparison studies using micro-tensile
or shear testing, the self-adhesive resin cements
nearly always showed lower bond strengths than
35
en - uTBS
30 den - uTBS
en - shear
25
den - shear
20
15
10
5
0
Unicem Panavia
Fig. 9. Bond strength (micro-tensile versus Shear) for enamel and
dentin comparing Unicem self-adhesive cement to Panavia self-
etching resin cement (averaged data from Abo-Hamar et al. 2005;
De Munck et al. 2004; Goracci et al. 2006; Luhrs et al. 2009; Sarr
et al. 2009; Yang et al. 2006).
ª 2010 Blackwell Publishing Ltd

non-self-adhesive resin cements (51). The same is true
of the relationship between any of the resin cements
and the GIC, the latter demonstrating bond strengths to
enamel or dentin that are typically one-half to one-
third of that of the resin cements (46, 52).
When tested with a pre-etching of enamel by
phosphoric acid, Unicem was shown to have higher
bond strength than when tested without pre-treatment
(35Æ6 versus 19Æ6 MPa), presumably because of the
enhanced microscopic irregularities produced by the
stronger acid compared to that produced by the cement
itself (38). But a lower bond strength was shown to
dentin when the phosphoric acid pre-etch was applied
(5Æ9 versus 15Æ9 MPa). This negative effect of pre-
etching of dentin for self-etch adhesives has been
shown many times in the literature and is likely due to
the presence of a thick collageneous matrix created by
phosphoric acid demineralisation that is mostly impen-
etrable to the viscous cement, thus leaving a weak
interface (38). When tested without the pre-etch, self-
adhesive resin cements have been shown to produce
fairly strong bonds to dentin, despite the fact that they
do not form a classical hybrid layer and show minimal
interaction with the dentin substrate when evaluated
microscopically (38, 39, 49, 57).
Other interesting findings of note can be gleaned from
some of the different studies of bond testing. Abo-Hamar
et al. (52) found that most cements showed a reduction
in bond strength when subjected to thermal cycling, but
this was typically only significant when bonding to
enamel. In contrast, Piwowarcyzk et al. (53) showed a
reduced bond to dentin for several cements when aged
and then thermal cycled as opposed to simply ageing,
but Unicem was not affected by the additional thermal
cycling. Walter et al. (46) found similar bond strengths
to bovine coronal and root dentin for Unicem, Panavia F
and glass–ionomer. In contrast, Yang et al. (49) found a
reduced bond strength to deep or cervical human dentin
compared to superficial human dentin for Unicem and
Panavia F, as well as for SuperBond C&B, but all
cements were used in a self-cure mode only in this
study. It has been suggested that the high viscosity of the
cement may predispose to poor penetration into the
dentin surface and that adding pressure during cemen-
tation in the laboratory may better simulate clinical
conditions, resulting in higher bond strengths. Goracci
et al. (48) tested this hypothesis and confirmed it for
both self-adhesive (Unicem and Maxcem) and a self-
etch resin cement (Panavia F). Piworwarczyk et al. (53)
ª 2010 Blackwell Publishing Ltd
SELF-ADHESIVE CEMENTS 305
tested shear bond strengths of Unicem and Panavia F as
well as five other resin cements after 150-day storage in
water. They found that when the dual-cured cements
were light-cured, as opposed to self-cure only, the bond
strengths were higher for about half of the cements, but
not for Unicem or Panavia. This result is curious as it is
generally agreed that bonding is enhanced when the
cements are truly dual-cured, because of the enhanced
properties of the polymer produced by the higher degree
of conversion. However, this study only measured
properties after ageing for 150-days in water, and it is
possible that the degradation in bond strength occurred
for other reasons not related to the cure of the cement
itself, thus demonstrating a brand dependent effect.
In the laboratory of one of the authors (Ferracane
and Hilton, unpublished data), the micro-shear bond
strength to human dentin and enamel has been tested
for a variety of resin cements, including self-adhesive,
self-etch and glass–ionomer. These results showed
similar bonds to enamel for the resin cements, being
significantly greater than glass–ionomer with or with-
out pre-conditioning with polyacrylic acid. However,
the data also showed the bond to dentin to be generally
highest for the self-etch resin cements when compared
to the self-adhesive resin cements (Fig. 10).
Ceramics. There are few studies comparing the bond
strength of self-adhesive resin cements to ceramics.
Those that exist have used zirconia as the substrate
(58–63). Unicem was the only self-adhesive resin
cement to be tested in these studies, with the exception
of the latest study by Blatz et al. (63) in which Maxcem
(though this cement is no longer marketed), BisCem,
Clearfil SA Cement and G-Cem were also tested. All of
these studies tested the bond of the cements to zirconia
with the shear bond test method. While most studies
used either the cement or another composite (often
pre-cured) as the opposing substrate, one study used
metal disks and recorded very high strengths (62),
emphasising the importance of the substrates on bond
strength testing.
The data generally show that the bond strength of
Unicem to air-abraded zirconia is equivalent to that of
Panavia F and that the bond of both is enhanced by pre-
treating the ceramic with the Rocatec process (Fig. 11).
This also is generally true for other resin cements.
Recent work in the laboratory of one of the authors
(Ferracane and Hilton; unpublished data) testing the
bond strength in micro shear of MaxCem Elite cement
306 J . L . F E R R A C A N E et al.

40·00 to various surfaces showed relatively high bonds to cast

Dentin
35·00 Enamel
gold (type III), Ni-Cr alloy (Rexillium), zirconia ceramic
30·00 (LAVA), lithium disilicate ceramic (emax CAD) and
25·00
feldspathic porcelain (Vitablock), suggesting that this
cement would be acceptable for all of these substrates
20·00
(Fig. 12).
15·00
Two other self-adhesive resin cements, G-Cem and
10·00
Clearfil SA, were shown to bond well to air-abraded
5·00 zirconia (22Æ2 and 18Æ4 MPa, respectively), while others
0·00 (Maxcem and BisCem) showed poor bonding (3Æ0 MPa

ite

r
ne
l

f or less). Glass–ionomer, resin-modified glass–ionomer

l

m
m
ua

m
em

el

el
ua

el

El

ce
ce
-s

ce

tio
-s
-s

-d
-d

-c

ji-
ax

ni

di
k
G

ra
X3

ce
k

Fu
X3

on
in

and zinc phosphate were all shown to bond minimally

in

ib
til

ax
N

/c
til
N

al
ul
ul

M
C
M

w
M

to zirconia in comparison, rarely achieving shear bond

m
ce
ji-
Fu

strengths exceeding 6–7 MPa (59, 61, 62) and being

Fig. 10. Micro-shear bond strength of various self-adhesive particularly sensitive to ageing conditions (59, 61). One
cements compared to other resin adhesive cements and a glass– study also showed that extended ageing in water with
ionomer (unpublished data). thermal cycling significantly reduced the bond of
Unicem and Panavia F to air-abraded or silica coated
25 Air-abraded zirconia by 25–45% (62), but several others showed
Rocatec minimal effect of thermal cycling, especially when
20 Rocatec was used to enhance bonding and stability
(59–61). This difference may be related to the numbers
15
of thermal cycles and ageing times used in the studies,
as the study that used the most extreme conditions
(20K cycles and 180 days of ageing in water) showed
10
the most significant effect (62).
Thus, the data for self-adhesive resin cements in
5 terms of bonding to ceramics is confined to zirconia and
demonstrates a brand dependency. The most studied
0 material, Unicem, bonds well to this substrate, espe-
Unicem Panavia F cially when air abraded or silica coated, and in these
Fig. 11. Bond strength of self-adhesive cement (Unicem) and self- cases is equivalent to one of the most popular self-
etch resin cement (Panavia F) to air-abraded and silica-coated etching resin cements (Panavia F) and other resin
(Rocatec) surfaces (Data from Blatz et al. 2007, 2009; Kombuloglu adhesive cements. There is likely some deterioration in
et al. 2006; Piwowarczyk et al. 2005). bond strength during ageing in aqueous fluids, but it is
not possible to predict the effect this will have on
45 clinical retention based on these in vitro studies.
40
Micro shear bond (Mpa)

35 Metals. Little data exist on the adhesion of self-

30
adhesive resin cements to metals used for prosthetics.
25
Wolfart et al. (64) measured the retentive force for
20
noble alloy crowns to titanium abutments and
15
demonstrated that the self-adhesive resin cement,
10
5
Unicem, had retentive strengths as high as poly-
0 carboxylate cement, with both being stronger than
Rexillium eMax CAD Lava ceramic Vitablock Cast gold glass–ionomer, zinc phosphate or zinc oxide eugenol
ceramic ceramic
cements. Studies published in the orthodontic literature
Fig. 12. Micro-shear bond strength of MaxCem elite self-adhesive have examined Unicem for adhering brackets to enamel
cement to various substrates (unpublished data). surfaces and have found that the bond strengths were

ª 2010 Blackwell Publishing Ltd


poorer than other orthodontic adhesives and the
material could not be supported for this use (65, 66).
The analysis of the debonded surface showed that the
amount of cement left on the tooth was less for the self-
adhesive resin cement than for the typical orthodontic
adhesives, suggesting that the bond to the metal bracket
was not the problem and further emphasising that
bonding to unetched and uncut enamel was less
effective for Unicem. A study in one of the authors’
laboratory (unpublished data) showed bond strengths
exceeding 20 MPa in microshear (Fig. 12), but the
bond to the base metal alloy was significantly higher
than to the gold alloy. This outcome is fairly typical for
resin cements bonding to metals of varying nobility,
based primarily on the presence of the more retentive
oxide film on the former. In any case, it seems doubtful
that there should be significant concern over the bond
to metal alloys used for restorative dentistry, though as
always, questions linger over the durability of such
bonds.
Marginal adaptation ⁄ microleakage
Cement adhesion to various substrates is an important
property, but adequate bonding can be achieved in
cases where there is not a complete seal of the
tooth ⁄ restorative interface, thus leading to significant
clinical problems. Thus, the efficiency by which the
self-adhesive resin cements adapt to and seal margins is
critical for their success.
Bott and Hannig (67) reported that class I porcelain
inlays cemented into teeth with a compomer cement
(Dyract Cem) used with or without an adhesive primer
(Prime & Bond 2Æ1) showed excellent marginal adap-
tation after in vitro thermal cycling and mechanical
loading. The results were equivalent to those obtained
with a dual curing resin cement (Dual Cement) and a
chemical curing resin cement (Panavia 21). The spec-
imens were aged for 4 months in water before being
subjected to the thermal and mechanical loading, and
the authors noted that, in part, the excellent marginal
adaptation could be related to the water uptake and
subsequent hygroscopic expansion of the compomer
cement. Rosentritt et al. (68) reported on the marginal
fit of MOD ceramic inlays cemented with Unicem in
comparison with an etch-and-rinse adhesive cement
(Variolink II), a self-etch resin adhesive cement (Pana-
via F), a resin-modified glass–ionomer (Fuji Plus), and a
self-adhesive compomer cement used with a self-etch
ª 2010 Blackwell Publishing Ltd
SELF-ADHESIVE CEMENTS 307
adhesive (Dyract Cem Plus). After thermal and
mechanical cycling, marginal quality (by SEM) and
dye penetration showed equivalent results for Unicem,
Variolink II and Panavia F, while poorer marginal
adaptation and greater leakage were observed for
the resin-modified glass–ionomer and the compomer
cement.
More recently, Frankenberger et al. (69) investigated
the marginal integrity of ceramic inlays bonded with
two self-adhesive resin cements (Maxcem and Unicem)
compared with several other resin cements. All speci-
mens were subjected to thermal cycling and mechanical
loading, and marginal analysis by SEM showed a
general reduction in gap-free margins after stressing,
with Maxcem showing significantly poorer marginal
adaptation to enamel and dentin than all other
cements. While Unicem was equivalent to the best
performers on dentin, its per cent of gap-free margins to
enamel was poorer than five other resin cements that
employed a phosphoric acid enamel etch. Thus, this
poorer result to enamel seems consistent with the
minimal ability of these self-adhesive resin cements, as
well as the self-etching resin cements tested in this
study, to etch and subsequently interact with enamel
substrates compared to resin cements used with etch-
and-rinse adhesives. The contrasting results shown for
the Rosentritt et al. (68) and Frankenberger et al. (69)
studies were suggested by the latter authors to have
been attributed to the larger size of the restorations
used in their study.
In another study, Behr et al. (70) investigated the
marginal adaptation and seal against leakage of luting
cements for all-ceramic crowns with dentin margins
after in vitro thermal cycling and mechanical loading
and showed the self-adhesive resin cement, Unicem, to
be equal to or better than other resin cements.
Furthermore, when used in conjunction with a self-
etch adhesive, Prompt-L-Pop, no further improvement
in marginal adaptation or sealing was obtained.
Leakage and marginal gaps have also been evaluated
for Unicem when used to cement full gold crowns (71)
and porcelain veneers (72). In the Piwowarczyk study
(71), the crown margins included areas in both enamel
and dentin, but the Unicem showed equal or slightly
better marginal seal to both enamel and dentin
compared to an etch-and-rinse adhesive cement, a
self-etching adhesive resin cement, a conventional
glass–ionomer, a resin-modified glass–ionomer and a
zinc phosphate cement exposed to 4 weeks of ageing in
308 J . L . F E R R A C A N E et al.
water followed by thermal cycling. All cements showed
less leakage at enamel than dentin margins, including
Unicem. However, marginal gaps were higher for the
Unicem compared to the other cements (except Panavia
F). When tested with veneers, Unicem showed compa-
rable or better sealing to dentin than other resin
cements, but the opposite was true for enamel margins,
causing the authors to conclude that Unicem should
not be used for cementing ceramic veneers, unless a
separate etch was applied (72).
Thus, collectively these studies suggest that at least
one self-adhesive resin cement, Unicem, may show
nearly equivalent results to other resin cements in
terms of marginal sealing and adaptation when bonding
inlays or crowns, but that a separate phosphoric acid
etch of the enamel margins is likely to be beneficial,
especially if the cement is used for porcelain inlays.
Durability ⁄ support – cement and adhesion
Many of the studies cited previously included some
aspect of mechanical loading and ⁄ or ageing (water
storage and ⁄ or thermalcycling) before analysing the
marginal quality or leakage of the cements for various
restorative applications. Other studies have examined
the effect of fatigue loading on the failure of teeth
restored with restorations cemented with self-adhesive
resin cements. Ngo Uy et al. (73) compared three resin
cements to a self-adhesive resin (Unicem) and zinc
phosphate in terms of cement failure when subjecting
gold crowns to fatigue loading. While Unicem only
withstood more fatigue cycles than the zinc phosphate
cement before showing signs of failure (though not
significantly more), the number of cycles to failure did
not differ significantly for any of the resin cements,
except possibly Calibra. Failures were mainly found at
the tooth–cement interface for the resin cements but
more frequently at the crown–cement interface for
Unicem and zinc phosphate. Based on the historical
clinical success of zinc phosphate, the results of these
studies, taken by themselves, would suggest that any of
the resin cements would be expected to be as durable as
zinc phosphate to mechanical fatigue stresses in the oral
cavity.
Burke et al. (74) evaluated the compressive strength
of ceramic crown ⁄ tooth assemblies cemented with
Unicem and another resin cement and showed them
to be equivalent, with mean compressive fracture
resistance of 890 N and 760 N, respectively. These
forces are higher than maximum biting forces measured
in a large number of men (600 N) and women (400 N)
by Miyaura et al. (75). In another study, Unicem was
compared to Panavia F and zinc phosphate for Procera
alumina crowns which were subjected to 1Æ2 million
fatigue cycles in a chewing simulator before being
tested for fracture strength (76). Although all specimens
survived the dynamic loading, Panavia F was shown to
have the highest load to fracture, with Unicem being
significantly lower and equivalent to the zinc phos-
phate cement. In any case, the authors pointed out that
the crowns, independent of cement, exceeded the
expected intraoral forces and would therefore be
expected to survive clinical loading. The study also
measured leakage at the margins and showed it to be
significantly lower for Panavia F then Unicem, with
both being lower than the zinc phosphate. In a similar
study, Preuss et al. (77) evaluated the effect of luting
cement on the strength of endodontically treated, post-
restored teeth with ceramic crowns. The study did not
indicate a difference in load bearing capacity of Unicem
when compared to a zinc phosphate or a GIC.
Thus, the studies examining the fatigue and load
bearing ability of crowns cemented with one self-
adhesive resin cement, Unicem, suggest that this
material may be at best equivalent to other resin
cements and likely to be clinically successful in this
regard based on a comparison with conventional
cements, such as glass–ionomer and zinc phosphate,
when tested under the same conditions.
Biocompatibility
There have been very few studies on the biocompati-
bility of self-adhesive resin cements. De Souza Costa
et al. (78) compared the pulpal response to Unicem and
Variolink II when cementing class V composite inlays in
human teeth scheduled for extraction after 7 or
60 days. Remaining dentin thickness averaged about
400 lm for the cavities. For both cements, a slight to
moderate inflammatory response was seen with tissue
disorganisation, which contrasted with the control
teeth containing a calcium hydroxide liner under
Unicem. The inflammatory response was most severe
for Variolink II, which showed evidence of resin
components deep into the dentin as expected owing
to the use of a separate etch with phosphoric acid, and
the response was inversely related to the remaining
dentin thickness. The response to Unicem was minimal,
ª 2010 Blackwell Publishing Ltd

which correlates with its limited penetration into the
dentin substrate because of its lack of a pre-etching step
and its relatively high viscosity. In one case for Unicem
where a pulpal exposure occurred, a severe inflamma-
tory response ensued. No reparative dentin was formed,
and no bacterial infiltrate was seen for the resin
cements.
More recently, Ulker and Sengun (79) evaluated the
cytotoxicity of three self-adhesive resin cements (Bis-
cem, Maxcem and Unicem) when compared with two
other resin cements (Bistite II DC and Panavia F) using
a 3D pulp cell culture with a 500 lm dentin barrier
between the cements and the cells. Biscem produced
the greatest cytotoxic effect, followed by Panavia F,
Unicem and Bistite II DC, with Maxcem being the least
toxic of the resin cements. This result was in contrast
with that of De Mendonca et al. (80), in which Unicem
was found to be less cytotoxic than calcium hydroxide,
resin-modified glass–ionomer or adhesive resin cement.
The reason for this discrepancy is not readily apparent.
The minimal information about the biocompatibility
of the self-adhesive resin cements suggests that they
should be well tolerated by the dental pulp, as long as
there is sufficient underlying dentin to serve as a
barrier. However, because of their higher viscosity and
lack of aggressive etching of the dentin mineral, they
may actually be expected to be better tolerated than
resin cements that rely on separate etchants and
bonding agents to secure adhesion. This is borne out
by the few clinical assessments of one of these cements,
Unicem, which has shown low levels of pulpal prob-
lems as explained in the next section.
Table 2. Comparison of number of stages with conventional and
self-adhesive luting materials
Conventional resin Self-adhesive
luting materials luting materials
Isolate Isolate
Etch preparation with Mix luting material and
phosphoric acid apply to restoration
Wash Remove excess
Dry Light cure
Apply bonding agent
Air dry, ensuring that there
are no ‘puddles’ at internal angles
Light cure
Mix luting material and
apply to restoration
Remove excess
Light cure
ª 2010 Blackwell Publishing Ltd
SELF-ADHESIVE CEMENTS 309
The clinical considerations
Handling ⁄ ease of use of self-adhesive resin cements
The uptake by practitioners of resin luting cements has
traditionally been slow, with authors identifying this
lack of acceptance more than 15 years ago (81). This
lack of support may well be attributed to the perceived
technique sensitivity of resin-based cements, given the
large number of clinical stages that are necessary to
achieve a bond to the dentine of the tooth preparation
when using ‘conventional’ resin luting materials, let
alone the meticulous isolation which is needed
(Table 2).
Today, increasing numbers of restorative techniques
cannot be performed with traditional acid-based luting
materials and without the use of adhesive systems and
resin-based luting materials. In an extensive review of
luting materials of choice for a variety of ten indirect
clinical techniques including cementation of a cast
metal or metal-ceramic crown, ceramic inlay and cast
post and core (82), of the 30 options available, the
authors chose resin-based systems for a total of 18
clinical situations, glass–ionomer luting material for 5,
phosphate cement and resin-modified glass–ionomer
both for 3 and polycarboxylate for one. While this
‘straw poll’ may have limited scientific acceptability, it
does indicate the increasing diversity of the clinical
techniques to which resin luting materials may be
considered appropriate.
The excellent physical properties and the ability of
resin luting materials to facilitate ‘adhesive’ luting of
restorations are distinct clinical advantages, because the
clinician may not always be able to achieve an ideal
taper or crown height. In this respect, Zidan and
Ferguson (83) compared the retention, in vitro, of
complete crowns (with three different tapers) cemented
with four different cements, with the results indicating
that the retentive values of the adhesive resins at 24
degree taper was 20% greater than the conventional
cements at 6-degree taper. However, practitioners
prefer materials that are easy to use, and it has been
considered that ease of use facilitates improved perfor-
mance (84). It could therefore be considered that a
resin luting material that does not require the etching
and bonding steps presents distinct advantages to the
clinician when compared with traditional resin luting
materials in terms of ease of use and potential savings in
time and chairside costs (Table 2).
310 J . L . F E R R A C A N E et al.
Therefore, it may not be surprising to note the
increase in use of resin luting cements by practitioners
in the United Kingdom since the introduction of this
group of self-adhesive resin cements. The results of a
2002 survey of 1000 UK dentists indicated that 30%
routinely used zinc phosphate cement for cementation
of crowns, with fewer than 10%, stating that they used
resin-based luting materials routinely (85). In contrast,
the results of a similar survey carried out in 2008
indicated that increasing numbers of dentists stated that
they were now using resin cements in the placement of
metal-ceramic restorations (21Æ3%) and that 9Æ2% were
using a self-adhesive variant (unpublished data, Burke,
et al.).
The assessment of new techniques and materials in
the dental practice plays an important role in their
overall evaluation and acceptance by dentists (86, 87),
because ease of use may contribute to good perfor-
mance. Co-ordinated assessments of new materials by
practitioner-based research groups, typically teamed
with the research expertise available in academic
institutions, are becoming more common. Perhaps the
first such group was the Clinical Research Associates
(CRA), based in the U.S. More recently, other practice-
based research networks have evolved, including
Practice-based Research in Oral Health (PROH) in the
U.S. (88) and the Product Research and Evaluation by
Practitioners Panel (PREP) based in the U.K. (89–91).
A UK evaluation by thirteen members of the PREP
Panel used a 21-question questionnaire designed to
provide information on the handling and ease of use of
RelyX Unicem and the comparison of this material with
pre-study cementation materials (91). A total of 144
restorations were placed in the study, and RelyX
Unicem was rated higher by the evaluators for ease of
use than both the pre-trial resin-based cement and
‘conventional’ cements. Ninety-two per cent (n = 12)
of the evaluators considered that it was ‘very advanta-
geous’ for the material under evaluation not to require
etching and bonding prior to cementation. All the
evaluators stated that they would purchase the material
if available at average cost. None of the evaluators
reported any incidence of patients with post-operative
sensitivity following placement of restorations with the
material.
The results of the PREP Panel study are in broad
agreement with those reported in the July 2003 CRA
Newsletter, in which 64% of the 28 evaluators who
assessed the handling of RelyX Unicem stated that this
product would replace products that they had used
previously, with 96% of evaluators rating it as excellent
or good and worthy of trial by colleagues (92). The CRA
also assessed the clinical performance of RelyX Unicem
when used by 68 evaluators in the placement of 4820
restorations, with follow-up from a few months to
1 year (93). The incidence of post-operative sensitivity
was reported to be ‘very low’, and there was a very low
incidence of de-bonding (0Æ1%).
Clinical evaluation of the performance of self-adhesive resin
luting materials
There is a paucity of studies that assess the long-term
performance of self-adhesive luting materials, not
surprising, given the small number of studies which
evaluate the clinical performance of conventional
cements and resin luting materials.
The PREP Panel re-evaluated the restorations
placed using RelyX Unicem after 2 years (94). Ninety
of the original 144 restorations placed using RelyX
Unicem were reviewed, the mean age of the resto-
rations being 21 months. Four restorations (4%), all
in patients of one operator, were reported to have
failed at the time of this report. The reasons for these
failures were unconnected with the use of the resin
cement (root fracture, porcelain fracture and unre-
lated enamel chipping), and it was concluded that
restorations luted with RelyX Unicem were perform-
ing satisfactorily in UK general dental practice after
21 months, although it was agreed that a longer
evaluation period was needed.
A recent article reported on a 1-year clinical
evaluations of 43 IPS Empress** inlays luted with
RelyX Unicem and compared with a control group of
40 inlays luted with Variolink II with Syntac adhesive
(Ivoclar Vivadent**) (95). The control group displayed
significantly better results regarding colour match and
chipping of the inlay margins when compared to
Unicem, but there were no statistical differences
between the two groups over a further eight param-
eters, and all the inlays were clinically acceptable.
The authors concluded that RelyX Unicem showed
comparable clinical performance to the conventional
resin system.
A prospective clinical trial started in 2003 evaluated
the performance of 49 metal-based fixed partial
**Ivoclar Vivadent, Schaan, Liechtenstein.
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dentures at 3 years, luted with either RelyX Unicem
or zinc phosphate cement (96). The authors con-
cluded that the self-adhesive resin cemented group
performed comparably with the ‘well-established’ zinc
phosphate cement group. The authors, in reviewing
the literature on zinc phosphate cement, commented
that its performance seemed ‘astonishing’, given its
lower compressive strength than resin cements, its
high solubility and the potential for pulpal irritation
and microleakage.
The small number of studies examining the clinical
performance of RelyX Unicem and other self-adhesive
luting materials therefore appear to provide promising,
albeit early, results.
Laboratory studies with clinical relevance
The marginal adaptation of all-ceramic crowns luted
with RelyX Unicem was assessed after simulation of
5 years of oral stress (70) and compared to crowns luted
with a compomer-based luting material (Dyract Cem
Plus) used in combination with an adhesive system
(NRC P&B NT, Dentsply**) and a ‘conventional’ resin
luting material (Variolink II: Ivoclar Vivadent**) used
with the Syntac Classic adhesive system (Ivoclar
Vivadent**). The results indicated that, without any
conditioning or pre-treatment, RelyX Unicem showed
marginal adaptation to dentine which was comparable
to the established resin luting materials.
Trajtenberg et al. (97) compared the microleakage of
all-ceramic crowns (IPS Empress: Ivoclar Vivadent**)
luted with RelyX Unicem to two resin cements used
with their own self-etching primers, Multilink (Ivoclar
Vivadent**) and Panavia 2.0 (Kuraray America†). The
results indicated that crowns luted with Panavia and
RelyX Unicem showed the same percentages of micro-
leakage (0Æ76% and 1Æ78%, respectively) on enamel
surfaces, while Multilink-luted specimens exhibited
significantly greater microleakage (13Æ12%). Microleak-
age was greater at margins bonded to dentine.
Results of a laboratory study, in which all-ceramic
crowns were luted to standardised preparations on
extracted maxillary premolar teeth, have indicated that
dentine-bonded crowns luted with RelyX Unicem have
similar fracture strength as crowns luted with Mirage
ABC ⁄ FLC, a material that has shown satisfactory
clinical performance (98).
In an extensive study, Johnson et al. (99) assessed
the retention of metal-ceramic crowns luted with a
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SELF-ADHESIVE CEMENTS 311
variety of luting materials, including the original type
of RelyX Unicem (Applicap) and a recently intro-
duced more easily mixed paste–paste version (Click-
er). They also tested the self-adhesive resin luting
materials (which they termed self-adhesive modified
resin cements) Fuji CEM (GC America), iCEM (He-
reaus Kulzer, Armonk, NY, USA), Bis-Cem (Bisco,
Schaumberg, IL, USA) and Maxcem (Kerr‡). They
made 20-degree standardised preparations on groups
of extracted third molar teeth, placed and removed
provisional restorations to simulate the clinical expe-
rience and cemented the crowns using gentle finger
pressure. The copings were subjected to dislodgment
forces along the apico-occlusal axis until failure. The
results indicated that the bond of the newer,
paste ⁄ paste version of RelyX Unicem did not appear
to be as strong to dentine as the original version
(Applicap) but that self-adhesive resin luting materials
provided additional retention when this is desired and
that all the cements tested retained metal castings as
well as, or better than, zinc phosphate cement.
Summary
The result of this review of the chemical and physical
properties of self-adhesive resin cements would suggest
that these materials may be expected to show similar
clinical performance as other resin-based and non-resin
based dental cements. However, clinical evaluations are
few and short term, so drawing long-term conclusions
about the overall effectiveness of these cements in
dental practice is not yet possible. However, the
handling properties of these materials appear to be
excellent, and their acceptance by the profession is
increasing.
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Correspondence: Jack L. Ferracane, PhD, Professor and Chair, Restor-
ative Dentistry, Division Director, Biomaterials and Biomechanics,
Oregon Health & Science University, 611 S.W. Campus Drive,
Portland, OR 97239, USA. E-mail: ferracan@ohsu.edu
ª 2010 Blackwell Publishing Ltd